首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   3503篇
  免费   101篇
  国内免费   8篇
化学   2794篇
晶体学   24篇
力学   39篇
数学   170篇
物理学   585篇
  2023年   20篇
  2021年   29篇
  2020年   43篇
  2019年   53篇
  2018年   34篇
  2017年   20篇
  2016年   53篇
  2015年   46篇
  2014年   75篇
  2013年   157篇
  2012年   132篇
  2011年   201篇
  2010年   73篇
  2009年   95篇
  2008年   173篇
  2007年   180篇
  2006年   174篇
  2005年   214篇
  2004年   162篇
  2003年   125篇
  2002年   142篇
  2001年   111篇
  2000年   137篇
  1999年   47篇
  1998年   39篇
  1997年   34篇
  1996年   55篇
  1995年   29篇
  1994年   48篇
  1993年   36篇
  1992年   51篇
  1991年   44篇
  1990年   39篇
  1989年   39篇
  1988年   51篇
  1987年   41篇
  1986年   60篇
  1985年   54篇
  1984年   56篇
  1983年   30篇
  1982年   35篇
  1981年   34篇
  1980年   29篇
  1979年   31篇
  1978年   30篇
  1977年   26篇
  1976年   21篇
  1975年   32篇
  1974年   28篇
  1972年   21篇
排序方式: 共有3612条查询结果,搜索用时 15 毫秒
961.
A single-domain colloidal crystal with high transmission quality, prepared by a shear-induced process, was fixed as a hydrogel film by photopolymerization. Upon gelation, the original optical quality was almost perfectly preserved. By replacing the solvent, the gelled crystal could be converted to smaller lattice constant crystals without significant degradation in its transmission characteristics. The conversion results in a stop-band wavelength coverage across the entire visible light range.  相似文献   
962.
Summary The structural changes of drawn poly(ethylene terephthalate) are observed as a function of the temperature of heat-treatment and the angle between the fiber axis and the magnetic field, using with NMR. The results of this experiment show that the low stretched sample C-2 is structureless, but that samples C-3 and C-4 stretched higher than sample C-2 are the doublet structure, and that the more highly stretched sample C-5 is structureless again.The calculated line shapes are compared with the observed line shapes, and they are found in satisfactory agreement with the observed ones. From the results, it becomes clear that the condition of the occurrence of the doublet structure depends on the orientation of the benzene ring proton pair.
Zusammenfassung Die Strukturänderung von gestrecktem Polyäthylenterephthalat wurde mittels der NMR als Funktion der Wärmebehandlungstemperatur und des Winkels zwischen der Faserachse und dem magnetischen Feld beobachtet. Die Ergebnisse dieser Untersuchungen zeigen, daß die schwach gestreckte Probe C-2 strukturlos ist, während die stärker gestreckten Proben C-3 und C-4 eine Dublettstruktur haben.Eine noch stärker gestreckte Probe C-5 ist wiederum strukturlos. Die gerechneten Linienformen der NMR wurden mit den beobachteten Linienformen verglichen, und es wurde gefunden, daß die vorigen mit den letzteren genügend gut übereinstimmen. Es ist offenbar, daß es von der Orientierung des Protonenpaares des Benzolrings abhängig ist, ob die Dublettstruktur beobachtet wird.
  相似文献   
963.
The radiation-induced polymerization of binary systems consisting of glass-forming monomer and glass-forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by Tg (glass transition temperature) and Tv of the system (30–50°C higher than Tg), which turned to be functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass-forming systems were much affected by homogeneity of the polymerization system and the Tg of the glass-forming solvent. The composition and temperature dependences in the glycidyl methacrylate–triacetin system as a typical homogeneous polymerization system were studied in detail, and the polymerizations of hydroxyethyl methacrylate–triacetin and hydroxyethyl methacrylate–isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower Tg monomer and higher Tg solvent and the latter typifies a system consisting of higher Tg monomer and lower Tg solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass-forming systems could be explained by considering the product of the effect of the physical effect relating to Tv and Tg of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect.  相似文献   
964.
Zhao M  Ito Y  Tu P 《Journal of chromatography. A》2005,1090(1-2):193-196
A novel flavanone glycoside, (2S)-4',5,6,7-tetrahydroxyflavavone 6-O-beta-D-glucopyranoside was isolated from the ethyl acetate extract of the flowers of Carthamus tinctorium by high-speed counter-current chromatography (HSCCC). Using an optimized two-phase solvent system composed of ethyl acetate-methanol-water (5:1:5, v/v), target compound (52 mg) with purity of 98.0% was obtained from 2.0 g of sample by HSCCC in seven times run. The structure of the target compound was elucidated by means of spectroscopic methods including IR, MS, 1D and 2D NMR techniques.  相似文献   
965.
Single crystals of ZnO were grown at 1 050–1200°C by the oxidation of zine vapor which was continuously evolved at constant rate of 7.2 × 10?5 mol/min. Favourable flow rate of oxygen was 4.3–6.6 × 10?5 mol/min and was 1.2–1.8 times than theoretical value to oxidize zine vapor. The crystals grew larger with raising up growing temperature. Large crystals having maximum size of 2–4 mm ini diameter and 22 mm long were grown at 1200°C for 55 hours. The crystals were light gray and transparent. Representative forms of the crystals were both platelet with developed (100) face and hexagonal prism-type.  相似文献   
966.
Melanosomes in black and red human hair are isolated and characterized by various chemical and physical techniques. Different yields of 4-amino-hydroxyphenolanaline by HI hydrolysis (a marker for pheomelanin) and pyrrole-2,3,5-tricarboxylic acid by KMnO(4)/H(+) oxidation (a marker for eumelanin) indicate that the melanosomes in black hair are eumelanosomes, whereas those in red hair are mainly pheomelanosomes. Atomic force microscopy reveals that eumelanosomes and pheomelanosomes have ellipsoidal and spherical shapes, respectively. Eumelanosomes maintain structural integrity upon extraction from the keratin matrix, whereas pheomelanosomes tend to fall apart. The black-hair eumelanosomes have an average of 14.6 +/- 0.5% amino acids content, which is attributed to the internal proteins entrapped in the melanosomes granules. The red-hair melanosomes contain more than 44% of amino acid content even after extensive proteolytic digestion. This high content of amino acids and the poorly reserved integrity of red-hair melanosomes suggest that some proteins are possibly covalently bonded with the melanin constituents in addition to those that are entrapped inside the melanin species. Soluene solubilization assay indicates the absorbance of melanin per gram of sample, adjusted for the amino acid content, is a factor of 2.9 greater for the black-hair melanosomes than the red-hair melanosomes. Metal analysis reveals significant amounts of diverse heavy metal ions bound to the two types of melanosomes. The amount of Cu(II) and Zn(II) are similar but Fe(III) content is four times higher in the red-hair melanosomes. (13)C solid-state nuclear magnetic resonance spectra and infrared spectra are presented and are shown to be powerful techniques for discerning differences in the amino acid contents, the 5,6-dihydroxyindole-2-carboxylic acid:5,6-dihydroxyindole ratio, and the degree of cross-linking in the pigment. Excellent agreement is observed between these spectral results and the chemical degradation data.  相似文献   
967.
Yamamoto T  Ohta T  Ito Y 《Organic letters》2005,7(19):4153-4155
[reaction: see text] Arylboronic acids react with aldehydes in the presence of a base and a catalytic amount of a palladium(0) complex with chloroform, affording the corresponding secondary alcohols in good yields. General palladium complexes have no catalytic activity without chloroform. Chloroform is essential for this reaction, and palladium complex that was prepared from Pd(PPh3)4 with CHCl3 showed good catalytic acitivity as well.  相似文献   
968.
2-Methyl-3,3-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene was obtained as a chelate ligand for palladium(II) and platinum(II) complexes. Sulfurization of 2-methyl-1,3-diphosphapropene mainly gave 3-thioxo-1,3-diphosphapropene which bears a PC-PS skeleton and was used as a ligand of transition-metal complexes. A doubly-sulfurized product of the 1,3-diphosphapropene, 1,3-dithioxo-1,3-diphosphapropene, was isolated and characterized. The palladium(II) complexes containing the ligated 1,3-diphosphapropenes were used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.  相似文献   
969.
A series of 4-alkoxy-2-(1-piperazinyl)quinazoline derivatives was synthesized and evaluated for its ability to reverse a scopolamine-induced learned impairment in a one-trial passive avoidance task (antiamnestic activity). 2-(4-Allyl-1-piperazinyl)-4-pentyloxyquinazoline (4) showed more potent antiamnestic activity than such reference compounds as aniracetam, idebenone and bifemelane at a wide dose range (1-30 mg/kg]. Compound 4 also exhibited potent anticonvulsive and antihypoxic activities, and was selected as the most promising nootropic candidate agent.  相似文献   
970.
Three new acylated flavonol glycosides, cypellogins A (1), B (2) and C (3), along with eight known phenolic compounds, were isolated from the dried leaves of Eucalyptus cypellocarpa, and their structures were elucidated using spectroscopic methods, including 2D NMR experiments and chemical evidence.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号